Poly(styrene-co-N-maleimide) precursor and poly(styrene-co-N-maleimide)-block-polystyrene have been synthesized by quasiliving radical polymerization. Low molecular weight compounds with the sites specific for the complementary binding to the maleimide moieties via triple hydrogen bonds, 2,4-diamino-6-n-alkoxy(C-4, C-8, and C-12)-s-triazines, have been prepared. Hydrogen bonding between diaminotriazine and maleimide units in the copolymer-diaminotriazine mixtures has been investigated by FTIR. Microphase separated structure in the block copolymer-diaminotriazine mixtures has been confirmed by DSC. (c) 2006 Wiley Periodicals, Inc.